Mixed sulfite esters of phenols and glycols



United States Patent 3,179,685 MIXED ULFHTE ESTERS 0F PIENOILS AND GLYCUIS Winchester L. Hubbard, Woodbridge, Allen E. Smith,

Qxford, and Rupert A. Covey, Woleott, Conn, assignore to United States Rubber Qompany, New York, N.Y., a corporation of New Eersey No Drawing. Filed Dec. 19, 1962, Ser. No. 245,643 3 (Ilairns. (@l. hide-456) The chemicals of the present invention may be represented by the general formula Ephe ine in which R is an aliphatic radical, e.g. alkyl, alkenyl, alkynyl, cycloalkyl, cyanoalkyl, or haloalkyl radical; R is an aromatic radical, e.g. phenyl, or naphthyl, or a phenyl or a naphthyl (aryl) radical having one or more substituents in the aryl nucleus selected from the group consisting of alkyl having up to 9 carbon atoms, cycloalkyl,

haloalkyl, alkoxy and halo; n is 2 to lb, and m is 1 to 10. Where m is greater than 1, the repeating oxyalkyl groups may be the same or different. Examples of R are alkyls having up to 18 carbon atoms, e.g. methyl, 9

ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.- butyl, amyl, hexyl, Z-ethylhexyl, octyl, decyl, isodecyl, dodecyl, hexadecyl octadecyl, allyl, methallyl, alkynyl radicals having 3 to 10 carbon atoms, e.g. propargyl and 1-(3-nonynyl), cyclohexyl, Z-cyanoethyl, chloroalkyls having up to 5 carbon atoms and up to 3 chloro radicals, e.g. Z-chloroethyl, 2,2,2-trichloroethyl, -chloropropyl, 6-chlorobutyL .w-trichloroarnyl. Examples of R are phenyl, l-naphthyl, Z-naphthyl, p-tolyl, o-tolyl, isopropyL- phenyl, tert.-butylphenyl, tert.-amylphenyl, nonylphenyl, cyclohexylphenyl, chloromethylphenyl, methoxyphenyl, and haloaryl having up to 5 halo radicals, e.g. bromophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl. Examples of the OC H group are ethyleneoxy, trimethyleneoxy, tetrarnethyleneoxy, propyleneoxy, isopropyleneoxy, 1,2-di1nethylethyleneoxy, octamethyleneoxy.

The preparation of the chemicals of the invention may be carried out by reacting the selected phenol with the separately prepared chlorosulfinate of the selected glycol ether, which may be made by reacting the selected glycol ether with thionyl chloride. The glycol ether may be made by reacting the selected alcohol, with one to ten moles of the selected alkylene oxide per mole of the alco hol. Such preparation is illustrated by the following reactions With the same symbols R, R and m as in the above general formula and for convenience using ethylene oxide (11:2) as the allcylene oxide:

II R 0 CH2CHg)OSCl H01 ice s bad Reaction (1) above is a well known and smooth reaction giving a mixture of products having varying numbers of alkylene oxide units. If a compound with a specific number of alkylene oxide units is desired, the mixture may be fractionated. The following reaction of isopropyl alcohol with propylene oxide is illustrative of the well known preparation of the starting glycol ethers according to reaction (1) above:

lsopropyl alcohol (153 ml., 120 g., 2.0 moles) and 2.4 g. sodium hydroxide were combined and refluxed While 203 ml. (174 g., 3.0 moles) propylene oxide were added during six hours. The temperature of the refluxing solution at the end of the addition was 55. Refluxing was continued for eight hours more during which time the reflux temperature rose to 108. The mixture was distilled to give 52 g. (44%) isopropoxyisopropyl alcohol, B.P. 147-148, 29 g. (16%) diisopropoxyisopropyl alco- 1101, B1 l13-127 (23 mm.), and 22 g. (9%) triisopropoxyisopropyl alcohol, HP. l53-163 (22 mm.).

The preparation of the chlorosulfinates of the glycol ethers according to reaction (2) is carried out at a temperature of between -5 C. and C., preferably near 0 C., and the yield of chlorosulfinate is nearly quantitative. An inert solvent such as benzene, xylene or solvent naphtha maybe used. This is illustrated in Exampic I below.

The preparation of the sulfite esters is carried out in the presence of an I-lCl acceptor, such as pyridine, dimethyl aniline or trimethylamine, and in a solvent such as benzene, xylene or solvent naphtha. The reaction temperature is generally between 10 C. and C., preferably near 0 C. This is illustrated in Example I below.

Examples of the sulfite diestcrs of the present invention are:

Phenyl methoxyethyl sulfite Phenyl ethoxyethyl sulfite Phenyl butoxyethyl sulfite Phenyl tert.-butoxyethyl sulfite Phenyl Z-ethylhexoxyethyl sulfite Phenyl hexadecoxyethyl sulfite l henyl cyclohexoxyethyl sulfite Phenyl Z-ethylhexoxyisopropyl sulfite Phenyl octoxyisopropoxyisopropyl sulfite Phenyl decoxytetraisopropoxyisopropyl sulfite Phenyl 3-isodecoxypropyl sulfite l-naphthyl octadecoxyisopropyl sulfite 2-naphthyl dodecoxypropyl sulfite Z-naphthyl 3-methoxy-2-butyl sulfite p-Tolyl 4-isopropoxy-1-hexyl sulfite p-tert.-Butylphenyl octadeooxyethyl sulfite Phenyl fi-chloroethoxyethyl sulfite p-tert.-Butylphenyl B-cyanoethoxyisopropyl sulfite m-Chlorophenyl l3-chloroethoxy-2-butyl sulfite o-Cyclohexylphenyl ethoxyisopropyl sulfite p-Chloromethylphenyl decoxyethyl sulfite p-Methoxyphenyl isobutoxy-Z-butyl sulfite 2,4-dichl0rophenyl methoxyethyl sulfite The following examples illustrate the invention. All parts and percentages referred to herein are by weight.

EXAMPLE I Preparation of o-tolyl isodecoxyethyl sulfite Isodecoxyethyl chlorosulfinate was prepared as illus- 3,17aesa trated in reaction (2) above as follows: thionyl chloride (45.4 ml., 74.4 g.; 0.625 mole) was added dropwise during one hour to 101 g. (0.5 mole) isodecoxyethyl alcohol prepared according to reaction (1) as illustrated above and previously cooled to C.5 C. The temperature during the addition was maintained below 5 C. the reaction mixture was allowed to warm to room temperature and stand for hours. The mixture was warmed to 50 C. (0.35 mm.) in order to remove dissolved gases and excess thionyl chloride. Yield, 143 g. (100%).

o-Cresol (5.9 g., 0.055 mole), 4.1 ml. (4.0 g., 0.05 mole) pyridine and 30 ml. xylene were combined and the solution was cooled to 0-5 C. A solution of 14.2 g. (0.05 mole) isodecoxyethyl chlorosulfinate in 40 ml. xylene was added during min. keeping the reaction temperature below 5 C. The mixture was stirred for one hour, washed twice with ml. portions of water and then stirred for one hour with 50 ml. 2 N NaOH. The organic layer was then washed several times with saturated salt solution until the washings were neutral to pH paper. The xylene was removed under reduced pressure and the residue heated to 182 (0.12 mm). The product was filtered through Dicalite (filter-aid) yielding 13.8 g. (78% yield) of o-tolyl isodecoxyethyl sulfite as a reddish-yellow oil; 12 1.4858.

Analysis.Calculated for C H O S: C, 64.01; H, 9.05; S, 9.00. Found: C, 64.19, 63.95; H, 9.21, 9.04; S, 8.67, 8.96.

EXAMPLE ll Preparation of p-tolyl isopropoxyisopropoxyisopropyl sulfite Isopropoxyisopropoxisopropyl chlorosulfinate was prepared as illustrated in reaction (2) above as follows: thionyl chloride (901111., 14.8 g., 0.125 mole) was added dropwise to 17.6 g. (0.1 mole) diisopropoxyisopropyl alcohol previously cooled to 05 C. The temperature during the addition was kept below 10 C. The mixture was stirred for two hours and then warmed to C. I

(0.5 mm.) to remove dissolved gases and excess thionyl chloride. Yield, 24.0 g. (93%).

p-Cresol (4.3 ml., 4.4 g., 0.04 mole), 3.3 ml. (3.2 g., 0.041 mole) pyridine and 20 ml. xylene were combined and the solution was cooled to 05 C. A solution of 10.6 g. (0.041 mole) isopropoxyisopropoxyisopropyl chlorosulfinate as described above in 30 ml. xylene was added during 20 min. keeping the reaction temperature below 10 C. The mixture was stirred for 15 min. and then washed twice with 25 ml. water, once with m1. 2 N NaOH, and twice with 25 ml. saturated salt solution (until washings were neutral). The xylene was removed under reduced pressure and the residue distilled to give 10.9 g. (81% yield) of p-tolyl isopropoxyisopropoxyisopropyl sulfite; B.P. 118157 (0.3 mm.), 11 1.4578.

Analysis.Calculated for C H O S: S, 9.71. Found: S, 8.68, 8.75.

EXAMPLE III This example illustrates the pre-emergence control of weeds.

To evaluate the chemicals of the invention as preemergent herbicides a measured amount teaspoon) of a mixture of weed seeds is spread evenly over the surface of a sandy-loam soil contained in a 6 inch pot. The weed seed mixture is made up of five broadleaved species, namely, pigweed (Amaranthus spp.), purslane (Portulaca spp.), quickweed (Galinsoga spp.), ragweed (Ambrosia spp.) and lambsquarters (Chenopodium spp.) and three grass types, namely crab grass (Digitaria spp.), barnyard grass (Echinochloa spp.) and foxtail (Setaria spp.). The seed is covered with A to A5" of soil and the chemical dispersed in water is spread evenly over the soil surface. Application of 40 mg. of chemical per pot is equivalent to a rate of 20 lbs. per acre. The pots are placed in the 4 greenhouse in 6 inch saucers and waterings are made from the bottom. Duplicate pots are run for each chemical and the eilectiveness of the compound is determined three weeks later by estimating the percent kill of the weeds compared to the untreated check pots. The weed control of the chemical of Example 11 at 20 lbs. per acre rate for broadleaved weeds was 50%.

EXAMPLE IV This example illustrates the post-emergence control of weeds.

To evaluate the chemicals of the invention as postemergent herbicides a measured amount teaspoon) of the weed seed used in Example III is spread evenly over the surface of a rich sandy-loam soil contained in a 4" x 4" x 4" box. The germinating seeds are maintained under a 16-hour light and an 8-hour dark exposure per 24-hour period and at a temperature of F. for 10 days. At this time the broadleaved weed species are approximately 1 /2" tall and the grassy weed species have leaves 4" to 5 long. Duplicate boxes of weeds are sprayed to runoff with aqueous dispersions of the chemicals at a concentration of 2,000 parts per million, the aqueous dispersions containing a small amount, about 0.01%, of a surface-active dispersing agent which is a reaction product of ethylene oxide and an alkyl phenol. The eiiectiveness of the compounds is determined after 10 days by estimating the percent control of the weeds compared to the untreated check boxes. The chemical of Example I gave control of broadleaved weeds and 30% control of grasses. The chemical of Example 11 gave control of broadleaved weeds and 97% control of grasses.

EXAMPLE V The following illustrates the insecticidal activity of the chemicals of the invention in tests against the larvae of Aedes aegypti (L.) mosquitoes. Fourth instar larvae were used. These larvae normally reach this stage in 5 days at 80 F. after hatching.

To 10 mgs. or" each chemical to be tested was added 1 ml. of acetone and 100 ml. of Water to give a concentration of 100 parts per million (p.p.rn.).

Twenty-five ml. aliquots. replicated once, of each chemical to be tested at a concentration of 100 ppm. and of checks without the chemical and of plain water checks were placed in test tubes and from 5 to 25 larvae were added. The tubes were held at 70 F. in darkness for 72 hours. At the end of this period the live and dead larvae were counted and the percent mortality calculated. All the larvae were alive in the checks (0% mortality). The percent mortality of the larvae treated with the chemicals of Examples I and 11 was 100% in each case.

The chemicals of the present invention may be applied to the soil or to plants as a dust in admixture with a powdered solid carrier, such as the various mineral silicates, e.g., mica, talc, pyrophyllite and clays, or as a spray in aqueous suspension or solution, preferably with the addition of a surface-active dispersing agent. The chemicals of the invention may be applied as an aqueous emulsion prepared by dissolving in a suitable solvent such as kerosene, fuel oil, diesel oil or xylene containing a surface-active dispersing agent, and adding such concentrate to water. Such surface-active dispersing agent maybe anionic, non-ionic or cationic, as shown in US. Patent 2,556,665, columns 2 to 4. The chemicals of the invention may also be admixed with powdered solid carriers, such as mineral silicates, together with a small amount of such a surface-active dispersing agent so that a readily wettable powder may be obtained which may be applied directly to plants, or which may be shaken up with water, to readily prepare a suspension of the chemical (and powdered carrier) in water for application in that form.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. A chemical represented by the general formula m in which R is selected from the group consisting of alkyl having up to 18 carbon atoms, allyl, methallyl, alkynyls having 3 to 10 carbon atoms, cyclohexyl, cyanoethyl, and chloroalkyls having up to 5 carbon atoms and up to 3 chloro atoms, and R is selected from the group consisting of phenyl, naphthyl, phenyl and naphthyl having substituents consisting of up to 5 halo radicals selected 6 from the class consisting of bromo and chloro, and monosubstituted phenyl and naphthyl having the substituent selected from the group consisting of alkyl having up to 9 carbon atoms, cyclohexyl, chloromethyl and methoxy, n is 2 to 10, and m is 1 to 10.

2. o-Tolyl isodecoxyethyl sulfite. 3. p-Tolyl isopropoxyisopropoxyisopropyl sulfite.

References Cited by the Examiner UNITED STATES PATENTS 2,820,808 1/58 Harris 260-456 CHARLES B. PARKER, Primary Examiner. 

1. A CHEMICAL REPRESENTED BY THE GENERAL FORMULA 